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Publication numberUS4100047 A
Publication typeGrant
Application numberUS 05/731,144
Publication date11 Jul 1978
Filing date12 Oct 1976
Priority date12 Oct 1976
Publication number05731144, 731144, US 4100047 A, US 4100047A, US-A-4100047, US4100047 A, US4100047A
InventorsWilliam H. McCarty
Original AssigneeMobil Oil Corporation
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Ultraviolet curable aqueous coatings
US 4100047 A
Abstract
Ultraviolet curable aqueous coating solutions are provided in which an hydroxy functional ethylenically unsaturated material, such as hydroxy ethyl acrylate or a polyether or polyester thereof, is dissolved in water with the aid of an amine photoinitiator and a photosensitizer is incorporated in the composition, preferably by reacting the hydroxy functionality in the ethylenically unsaturated material with a tetracarboxylic acid dianhydride including a proportion of benzophenone tetracarboxylic dianhydride which provides the needed ultraviolet photosensitizer.
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Claims(12)
I claim:
1. An ultraviolet curable aqueous coating solution comprising an hydroxy functional ethylenically unsaturated ultraviolet curable material reacted with a polycarboxylic acid or anhydride and dissolved in water with the aid of an amine photoinitiator, said ultraviolet curable material being monoethylenic or polyethylenic and monohydric or polyhydric and having a molecular weight providing a viscosity ranging from a fluid liquid to a viscous semi-solid, the proportion of said polycarboxylic acid or anhydride providing an acid number of from 20-300, and said amine providing a pH of from 6.0-11.0, said solution further containing a photosensitizer rendering the composition sensitive to ultraviolet light.
2. An ultraviolet curable aqueous coating solution as recited in claim 1 in which an hydroxy functional polyethylenically unsaturated material which is resinous is reacted with a polycarboxylic acid monoanhydride.
3. An ultraviolet curable aqueous coating solution as recited in claim 2 in which said resinous material is an epoxy resin diacrylate.
4. An ultraviolet curable aqueous coating solution as recited in claim 1 in which the hydroxy functional ethylenically unsaturated material is a monoacrylate and said polycarboxylic acid is a dianhydride.
5. An ultraviolet curable aqueous coating solution as recited in claim 4 in which said dianhydride is benzophenone tetracarboxylic dianhydride providing from 5%-40% of the anhydride functionality.
6. An ultraviolet curable aqueous coating solution as recited in claim 4 in which the unsaturation is acrylic.
7. An ultraviolet curable aqueous coating solution as recited in claim 1 in which said amine photoinitiator is ethylenically unsaturated.
8. An ultraviolet curable aqueous coating solution as recited in claim 7 in which said amine photoinitiator is dimethylamino ethyl acrylate.
9. An ultraviolet curable aqueous coating solution comprising the reaction product of an hydroxy acrylate with an approximately stoichiometric proportion of tetracarboxylic dianhydride consisting essentially of benzophenone tetracarboxylic acid dianhydride, said reaction product being dissolved in water with the aid of a tertiary amine photoinitiator.
10. An ultraviolet curable aqueous coating solution as recited in claim 9 in which said hydroxy acrylate is selected from hydroxy C2 - C4 alkyl acrylates and hydroxy ethers or esters thereof containing an average of from 2-10 ether or ester groups per molecule, and said reaction product is formed with a stoichiometric proportion of anhydride groups.
11. An ultraviolet curable addition reaction product of hydroxy C2 - C4 alkyl monoacrylate and hydroxy ethers or esters thereof, with an approximately stoichiometric proportion of tetracarboxylic acid dianhydride comprising benzophenone tetracarboxylic acid dianhydride providing from 5% to 40% of the anhydride functionality.
12. An ultraviolet curable addition product as recited in claim 11 neutralized with a tertiary amine.
Description

The present invention relates to water solution coating compositions capable of curing on ultraviolet light exposure, and particularly to compositions in which either the photosensitizer or the photoinitiator, and preferably both, are directly incorporated into the cured coating so as to better resist loss by volatilization or extraction.

In accordance with this invention, an hydroxy functional ethylenically unsaturated ultraviolet curable material is reacted with a polycarboxylic acid and preferably an anhydride thereof to provide pendant carboxyl groups enabling dispersion in water with the aid of an amine which serves as the photoinitiator. In preferred practice, the polycarboxylic acid anhydride is selected to provide the photosensitizer and the amine may be ethylenically unsaturated so that these components become chemically coupled with the ultraviolet curable material upon exposure to ultraviolet light.

The hydroxy functional ethylenically unsaturated ultraviolet curable material may vary considerably in this invention. In conventional practice, the ultraviolet curable material is a liquid of coating viscosity and this creates a situation where this material includes volatile and/or toxic materials. It is desirable to provide as much resinification as possible in order to minimize volatility or toxicity, but this is inconsistent with the fluidity needed for coating application, and also with the desire to substantially eliminate volatile organic solvents.

In this invention greater resinification is permitted because of dispersion in water, and this permits the problem of volatile and toxic ethylenically unsaturated materials to be avoided independently of the selection of the material.

The ethylenically unsaturated ultraviolet curable material may be monoethylenic or polyethylenic, the preferred unsaturation being acrylic because acrylic unsaturation exhibits an excellent ultraviolet cure. Similarly, the ultraviolet curable material may be monohydric or polyhydric and the molecular weight may be low enough to provide a fluid liquid, or high enough to provide a solid or viscous semi-solid.

When the molecular weight is sufficient to provide a resinous body, as in epoxy resin diacrylates which are polyhydric, the polycarboxylic acid anhydride is preferably a monoanhydride, such as trimellitic anhydride, glutaric anhydride or maleic anhydride. On the other hand, when the molecular weight of a polyethylenic material is low (normally liquid) or when the radiation curable material is monoethylenic, then dianhydrides can be used to increase both molecular weight and ethylenic functionality. Thus, hydroxy ethyl acrylate can be reacted with an approximately stoichiometric proportion of tetracarboxylic acid dianhydride, such as pyromellitic dianhydride to form dicarboxylic diacrylate diesters. The stoichiometry is between the anhydride group and the single hydroxy group in the hydroxy acrylate, and it can vary 20%. If desired, polyhydric materials can be advanced in molecular weight by reaction with a small amount of organic polyisocyanate, like toluene diisocyanate, at the expense of some of the hydroxy functionality.

Other ethylenically unsaturated ultraviolet curable materials are illustrated by pentaerythritol triacrylate, hydroxy propyl acrylate, and unsaturated hydroxy functional polyesters containing maleic acid or anhydride. The acrylates can be replaced by methacrylates, norbornenes, and the like.

The dianhydride which is preferred in this invention is benzophenone tetracarboxylic dianhydride since this not only allows an increase in ethylenic functionality, but it introduces a ketonic photosensitizer which is chemically united to the ethylenically unsaturated material so that it becomes an integral part of the final cured product. In preferred practice using monoacrylates, the benzophenone dianhydride will provide from 5% - 40%, preferably from 8% - 20%, of the anhydride functionality.

The reaction between the hydroxy functional ethylenically unsaturated material and the anhydride is a simple addition reaction which is fostered by moderate heat (30-150 C.) and a small amount (0.2-3%) of a basic catalyst (typically a tertiary amine, such as triethyl amine). A trace of a polymerization inhibitor, such as benzoquinone, may also be present to minimize inadvertent polymerization.

The reaction with the anhydride is easily followed by observing the acid number decrease as the reaction proceeds.

While the anhydride can react by addition without causing any reaction with carboxyl functionality, the acid itself can be used, e.g., a phthalic acid or mellitic acid, but it is difficult to stop the reaction with only one ester group per molecule, so the use of anhydride is much preferred. Also, milder reaction conditions are used which helps to avoid polymerization.

The proportion of polycarboxylic acid or anhydride thereof can vary considerably. Generally, one starts with an ethylenically unsaturated hydroxy functional material which is poorly soluble in water, and the reaction with anhydride introduces carboxyl functionality which permits dispersion in water with the aid of a base, preferably an amine. All that is required is to use enough anhydride to enable water dispersibility, preferably water solubility. On this basis, a final acid number of from 20-300, preferably from 60-200, is adequate to provide the desired result.

It is not desired to introduce a large amount of water. Resin solids contents of at least 40%, preferably at least 60%, are contemplated herein. Of course, these solutions may be pigmented as desired, dyed, and they may include diverse materials such as wetting agents, flow control agents, and even dissolved or suspended resins which are not unsaturated, including aminoplast resins such as hexamethoxy methyl melamine, to enable a subsequent thermal cure.

The acidic material produced as previously noted is associated with water with the aid of a base which is preferably an amine, such association being itself entirely conventional. Enough base is used to provide the desired dispersion, and this will vary depending upon the acid number and the particle size desired in the usually colloidal solutions which are produced. A pH of from 6.0 - 11.0 are generally contemplated, preferably a pH of from 7.5 - 10.5.

The point to be observed is that the amine which is used to neutralize the acidity of the unsaturated material provides both water dispersibility and photoinitiation. The photoinitiator effect of amines, and especially tertiary amines such as dimethyl ethanol amine, is well known.

A feature of this invention is to employ an ethylenically unsaturated amine, preferably a tertiary amine, to provide the dual function noted above. Preferred unsaturated amines are illustrated by dimethylamino ethyl acrylate, but the methyl groups can be replaced by other lower (C1 - C4) alkyl groups and the ethyl acrylate can be replaced by propyl or butyl acrylate or the corresponding methacrylates. This provides a photoinitiator which polymerizes on ultraviolet exposure so as to better resist removal by volatilization or extraction.

This invention particularly contemplates water solutions of high solids content, and these are provided by employing liquid monoethylenically unsaturated hydroxy functional polyethers, preferably those made by reacting several moles of propylene oxide with acrylic acid or hydroxyethyl acrylate.

The liquid monoethylenically unsaturated hydroxy functional polyethers which are preferably used herein are more fully disclosed in the application of Marvin L. Kaufman, Ser. No. 618,101, filed Sept. 30, 1975. As described in that application, a monoethylenic carboxylic acid or hydroxy ester thereof, and especially acrylic acid or hydroxy alkyl acrylate such as hydroxy ethyl acrylate, is reacted with enough alkylene monooxide (preferably propylene oxide) in the presence of a Lewis acid catalyst such as boron trifluoride etherate, to produce an hydroxy functional polyether, preferably containing an average of 2-10 ether groups per molecule. This invention will be illustrated by a polyether formed by adducting an average of 5 moles of propylene oxide onto one mole of hydroxyethyl acrylate, all of the hydroxy functional products provided in the disclosure of said application Ser. No. 618,101 being useful herein, and the disclosure of that application is hereby incorporated by reference.

The invention is illustrated in the following examples.

EXAMPLE 1

Charge a dry reaction vessel fitted with a stirrer, thermometer, condenser, drying tube and two additional funnels with 928g hydroxyethyl acrylate (8.8 moles). Add enough boron trifluoride etherate to initiate the reaction, approximately 1 ml. Then, with suitable cooling, add 2320g propylene oxide (40.0 moles) and additional BF3 etherate (15-20 ml.) at such a rate so as to maintain reaction temperature at 50 C. Total addition time is 2-2.5 hours. Maintain the temperature as high as possible by decreasing cooling. When the temperature drops to about 40 C., sample the reaction for gas chromatography. When gas chromatography shows no propylene oxide, add 0.32g hydroquinone (100 parts per million) and 2 ml. triethylamine to stabilize the product. The product is a clear, light yellow liquid of 35-40 centipoise viscosity. A complete gas chromatography analysis indicates the product is a mixture of hydroxyethyl acrylate (˜2%) and adducts thereof having the formula shown below in which x ranges from 1 to about 10, and has an average value of 5. NMR analysis of the product shows the correct ratio of vinyl protons to the remaining types of protons and infrared analysis shows the presence of hydroxyl, acrylate unsaturation and ether bands, all consistent with the following structure: ##STR1##

EXAMPLE 2 Preparation of A Water Soluble-Ultraviolet Curable Coating Containing a Copolymerizable Ketonic Sensitizer

Charge a reaction flask fitted with a stirrer, condenser, thermometer, and nitrogen inlet with:

1. 406 grams HEA . 5 PO * (1.0 equivalent hydroxy of the product of Example 1)

2. 0.023 gram benzoquinone (polymerization inhibitor)

3. 25 grams benzophenone tetracarboxylic dianhydride (0.155 equivalence anhydride)

4. 92 grams pyromellitic dianhydride (0.845 equivalence anhydride)

5. 7.8 grams triethyl amine (about 1.5% by weight)

The mixture was heated at 70-75 for 5 hours. After this time, the acid number was 122 (theoretical = 107). Infrared analysis showed a small amount of anhydride to still be present.

Then add slowly:

6. 61.6 grams dimethyl ethanol amine

7. 250 grams distilled water.

The product was a water solution having a solids content of 70% and a Gardner-Holdt viscosity of E-F (140-160 cps). The viscosity of the solution product was stable for over one week at room temperature.

The material was drawn down onto a metal substrate and cured by passing under two 200 watt per inch medium pressure mercury lamps at 10 feet per minute in an air atmosphere. The cured film was no longer water soluble and was dry and nontacky.

EXAMPLE 3

The preparation and curing procedure described in Example 2 was repeated except that dimethylamino ethyl acrylate was substituted in step 6. The cured film obtained was similar to that obtained in Example 2, but the unsaturated amine did not volatilize or extract as easily as the dimethyl ethanol amine of Example 2.

When the benzophenone tetracarboxylic dianhydride (component 3 in Example 2) is omitted, then the ultraviolet cure requires the external addition of a photosensitizer such as methyl or butyl benzoin ether, and these systems are significantly less stable.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US3901779 *27 Aug 197326 Aug 1975Dow Chemical CoVinyl ester resin and process for curing same with ionizing radiation in the presence of amines
US3914165 *7 Jan 197421 Oct 1975Desoto IncRadiation curable non-gelled michael addition reaction products
US3926641 *11 Oct 197316 Dec 1975Sun Chemical CorpPhotopolymerizable compositions comprising polycarboxysubstituted benzophenone reaction products
US4004998 *25 Apr 197525 Jan 1977Sun Chemical CorporationPhotopolymerizable compounds and compositions comprising the product of the reaction of a hydroxy-containing ester and a monocarboxy-substituted benzophenone
US4022674 *12 May 197510 May 1977Sun Chemical CorporationPhotopolymerizable compounds and compositions comprising the product of the reaction of a monomeric ester and a polycarboxy-substituted benzophenone
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4303484 *22 Aug 19791 Dec 1981Shin-Etsu Chemical Co., Ltd.Photocurable organopolysiloxane compositions
US4612336 *22 Feb 198516 Sep 1986Dai-Ichi Kogyo Seiyaku Co., Ltd.Process for preparing water-soluble acrylic polymers by irradiating aqueous monomer solutions containing a surfactant
US4619964 *3 Oct 198328 Oct 1986Rohm And Haas CompanyStabilized aqueous copolymer dispersions
US4777276 *29 Oct 198111 Oct 1988Minnesota Mining And Manufacturing CompanyAcrylamidoacylated oligomers
US4837290 *11 Jul 19886 Jun 1989Minnesota Mining And Manufacturing CompanyAcrylamidoacylated oligomers
US4914223 *17 Aug 19883 Apr 1990Minnesota Mining And Manufacturing CompanyAcrylamidoacylated oligomers
US4996243 *16 Jan 199026 Feb 1991Minnesota Mining And Manufacturing CompanyCurable acrylamido oligomer compositions with initiator, and cured products
US5352326 *28 May 19934 Oct 1994International Business Machines CorporationProcess for manufacturing metalized ceramic substrates
US5512607 *6 Jun 199530 Apr 1996W. R. Grace & Co.-Conn.Unsaturated epoxy ester with quaternary ammonium and phosphate groups
US56164431 Jun 19951 Apr 1997Kimberly-Clark CorporationSubstrate having a mutable colored composition thereon
US56433565 Jun 19951 Jul 1997Kimberly-Clark CorporationInk for ink jet printers
US56437011 Jun 19951 Jul 1997Kimberly-Clark CorporationElectrophotgraphic process utilizing mutable colored composition
US56459645 Jun 19958 Jul 1997Kimberly-Clark CorporationDigital information recording media and method of using same
US568138019 Dec 199628 Oct 1997Kimberly-Clark Worldwide, Inc.Ink for ink jet printers
US568384322 Feb 19954 Nov 1997Kimberly-Clark CorporationSolid colored composition mutable by ultraviolet radiation
US5685754 *19 May 199511 Nov 1997Kimberly-Clark CorporationMethod of generating a reactive species and polymer coating applications therefor
US5686503 *22 Jan 199611 Nov 1997Kimberly-Clark CorporationMethod of generating a reactive species and applications therefor
US57008505 Jun 199523 Dec 1997Kimberly-Clark WorldwideColorant compositions and colorant stabilizers
US570995516 Oct 199620 Jan 1998Kimberly-Clark CorporationAdhesive composition curable upon exposure to radiation and applications therefor
US57212875 Jun 199524 Feb 1998Kimberly-Clark Worldwide, Inc.Method of mutating a colorant by irradiation
US57336932 Jan 199731 Mar 1998Kimberly-Clark Worldwide, Inc.Method for improving the readability of data processing forms
US5738916 *25 Oct 199614 Apr 1998Canon Kabushiki KaishaUltraviolet-curing composition, pattern forming method making use of the same, printed-wiring board and its production
US57391755 Jun 199514 Apr 1998Kimberly-Clark Worldwide, Inc.Photoreactor composition containing an arylketoalkene wavelength-specific sensitizer
US57475505 Jun 19955 May 1998Kimberly-Clark Worldwide, Inc.Method of generating a reactive species and polymerizing an unsaturated polymerizable material
US57731825 Jun 199530 Jun 1998Kimberly-Clark Worldwide, Inc.Method of light stabilizing a colorant
US578296327 Nov 199621 Jul 1998Kimberly-Clark Worldwide, Inc.Colorant stabilizers
US578613229 May 199628 Jul 1998Kimberly-Clark CorporationPre-dyes, mutable dye compositions, and methods of developing a color
US57980155 Jun 199525 Aug 1998Kimberly-Clark Worldwide, Inc.Method of laminating a structure with adhesive containing a photoreactor composition
US58111995 Jun 199522 Sep 1998Kimberly-Clark Worldwide, Inc.Adhesive compositions containing a photoreactor composition
US58374295 Jun 199617 Nov 1998Kimberly-Clark WorldwidePre-dyes, pre-dye compositions, and methods of developing a color
US58494115 Jun 199515 Dec 1998Kimberly-Clark Worldwide, Inc.Polymer film, nonwoven web and fibers containing a photoreactor composition
US585565515 Apr 19975 Jan 1999Kimberly-Clark Worldwide, Inc.Colorant stabilizers
US585858616 May 199712 Jan 1999Kimberly-Clark CorporationDigital information recording media and method of using same
US586547121 Dec 19942 Feb 1999Kimberly-Clark Worldwide, Inc.Photo-erasable data processing forms
US5869220 *6 Jun 19979 Feb 1999Macdermid Acumen, Inc.Waterborne photoresist emulsions and methods of preparation thereof
US588533731 Oct 199723 Mar 1999Nohr; Ronald SinclairColorant stabilizers
US589122931 Jul 19976 Apr 1999Kimberly-Clark Worldwide, Inc.Colorant stabilizers
US590849524 Sep 19971 Jun 1999Nohr; Ronald SinclairInk for ink jet printers
US600826822 Jan 199828 Dec 1999Kimberly-Clark Worldwide, Inc.Photoreactor composition, method of generating a reactive species, and applications therefor
US601747123 Apr 199725 Jan 2000Kimberly-Clark Worldwide, Inc.Colorants and colorant modifiers
US60176618 Oct 199725 Jan 2000Kimberly-Clark CorporationTemporary marking using photoerasable colorants
US60334655 Apr 19967 Mar 2000Kimberly-Clark Worldwide, Inc.Colorants and colorant modifiers
US60542563 Dec 199825 Apr 2000Kimberly-Clark Worldwide, Inc.Method and apparatus for indicating ultraviolet light exposure
US60602003 Feb 19989 May 2000Kimberly-Clark Worldwide, Inc.Photo-erasable data processing forms and methods
US60602233 Dec 19989 May 2000Kimberly-Clark Worldwide, Inc.Plastic article for colored printing and method for printing on a colored plastic article
US606355116 Nov 199816 May 2000Kimberly-Clark Worldwide, Inc.Mutable dye composition and method of developing a color
US60664393 Dec 199823 May 2000Kimberly-Clark Worldwide, Inc.Instrument for photoerasable marking
US607197926 Dec 19976 Jun 2000Kimberly-Clark Worldwide, Inc.Photoreactor composition method of generating a reactive species and applications therefor
US609023631 Dec 199718 Jul 2000Kimberly-Clark Worldwide, Inc.Photocuring, articles made by photocuring, and compositions for use in photocuring
US609962823 Jan 19978 Aug 2000Kimberly-Clark Worldwide, Inc.Colorant stabilizers
US61209493 Dec 199819 Sep 2000Kimberly-Clark Worldwide, Inc.Photoerasable paint and method for using photoerasable paint
US61270733 Dec 19983 Oct 2000Kimberly-Clark Worldwide, Inc.Method for concealing information and document for securely communicating concealed information
US61686546 Apr 19992 Jan 2001Kimberly-Clark Worldwide, Inc.Colorant stabilizers
US616865515 Dec 19982 Jan 2001Kimberly-Clark Worldwide, Inc.Colorant stabilizers
US617714424 Mar 199723 Jan 2001Basf Coatings AgBinder and its use in radiation-curable coating agents
US621138310 Feb 19983 Apr 2001Kimberly-Clark Worldwide, Inc.Nohr-McDonald elimination reaction
US622815720 Jul 19998 May 2001Ronald S. NohrInk jet ink compositions
US62350951 Jun 199922 May 2001Ronald Sinclair NohrInk for inkjet printers
US624205729 Apr 19985 Jun 2001Kimberly-Clark Worldwide, Inc.Photoreactor composition and applications therefor
US626545828 Sep 199924 Jul 2001Kimberly-Clark Worldwide, Inc.Photoinitiators and applications therefor
US62778973 Jun 199921 Aug 2001Kimberly-Clark Worldwide, Inc.Photoinitiators and applications therefor
US629469816 Apr 199925 Sep 2001Kimberly-Clark Worldwide, Inc.Photoinitiators and applications therefor
US633105624 Feb 200018 Dec 2001Kimberly-Clark Worldwide, Inc.Printing apparatus and applications therefor
US634230528 Dec 199929 Jan 2002Kimberly-Clark CorporationColorants and colorant modifiers
US636839512 May 20009 Apr 2002Kimberly-Clark Worldwide, Inc.Subphthalocyanine colorants, ink compositions, and method of making the same
US636839619 Jan 20009 Apr 2002Kimberly-Clark Worldwide, Inc.Colorants, colorant stabilizers, ink compositions, and improved methods of making the same
US648622719 Jun 200126 Nov 2002Kimberly-Clark Worldwide, Inc.Zinc-complex photoinitiators and applications therefor
US65035593 Jun 19997 Jan 2003Kimberly-Clark Worldwide, Inc.Neonanoplasts and microemulsion technology for inks and ink jet printing
US652437912 Jan 200125 Feb 2003Kimberly-Clark Worldwide, Inc.Colorants, colorant stabilizers, ink compositions, and improved methods of making the same
US786348510 Dec 20044 Jan 2011Omnitech Environmental, LlcAdditive and vehicle for inks, paints, coatings and adhesives
US818818430 Nov 201029 May 2012Omnitech Environmental, LlcAdditive and vehicle for inks, paints, coatings and adhesives
US20040180226 *19 Dec 200316 Sep 2004Subhankar ChatterjeeRadiation curable aqueous compositions for low extractable film packaging
US20060128831 *10 Dec 200415 Jun 2006Omnitech Environmental, LlcAdditive and vehicle for inks, paints, coatings and adhesives
US20110086957 *30 Nov 201014 Apr 2011Leroy John CookAdditive and vehicle for inks, paints, coatings and adhesives
EP0927154A1 *25 Aug 19977 Jul 1999Henkel CorporationPolyester oligomer acrylates
EP0927154A4 *25 Aug 199727 Jun 2001Henkel CorpPolyester oligomer acrylates
EP2593513A2 *7 Jul 201122 May 2013Invista Technologies S.a r.l.High dimensional stability polyester compositions
EP2593513A4 *7 Jul 201122 Jan 2014Invista Tech SarlHigh dimensional stability polyester compositions
WO1997041184A1 *24 Mar 19976 Nov 1997Basf Coatings AgBinder and its use in radiation-curable coating agents
Classifications
U.S. Classification522/65, 522/179, 523/412, 524/832, 522/182, 522/183, 522/84, 430/285.1, 524/845, 428/522, 522/103, 523/402
International ClassificationC08F299/04, C08G63/66, C08F2/50
Cooperative ClassificationC08F299/0428, C08G63/66, Y10T428/31935
European ClassificationC08G63/66, C08F299/04B6B
Legal Events
DateCodeEventDescription
5 Sep 1984ASAssignment
Owner name: VALSPAR CORPORATION THE 1101 EAST THIRD STREET SOU
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:MOBIL OIL CORPORATION A NY CORP.;REEL/FRAME:004309/0193
Effective date: 19840725